Shaped articles fabricated from polyamides comprising fluoroether functionalized aromatic moieties

ABSTRACT

The invention is directed to shaped articles fabricated from polyamides comprising fluoroether functionalized aromatic moieties. Particular polyamides include nylon 6, 6 and nylon 6 copolyamides that comprise fluoroether functionalized aromatic amide repeat units. The shaped articles hereof are characterized by reduced surface tension and are useful for imparting soil resistant films, molded parts, fibers, fabrics, and carpets.

RELATED PATENT APPLICATIONS

This patent application is related to U.S. patent applications Ser. Nos.13/166,006 and 13/166,052.

FIELD OF THE INVENTION

The invention is directed to shaped articles fabricated from polyamidescomprising fluoroether functionalized aromatic moieties. Particularpolyamides include nylon 6, 6 and nylon 6, copolyamides that comprisefluoroether functionalized aromatic repeat units.

BACKGROUND

Fluorinated materials have many uses. In particular, they are used inpolymer-related industries, and, more particularly, in fiber-relatedindustries, to impart soil and oil resistance. Generally, thesematerials are applied as a topical treatment, but their effectivenessdecreases over time due to material loss via wear and washing.

There is a need to provide polymeric materials that have improved soiland oil resistance.

SUMMARY OF THE INVENTION

In one aspect, the invention provides a polymer comprising a fluoroetherfunctionalized aromatic repeat unit represented by the structure (I)

wherein,α is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen;Ar represents a benzene or naphthalene radical;each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl;OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II);wherein one or more carbons can be replaced by ether oxygen;X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the structure (Ia)

-   -   wherein q=0-10;    -   Y is O or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂.

In another aspect, the present invention provides a process, comprisingcombining in a pressure vessel a fluoroether functionalized aromaticdiester or diacid with a C₄-C₁₂ diamine, branched or unbranched, to forma reaction mixture; sealing said pressure vessel, and heating saidreaction mixture in an oxygen reduced atmosphere to a temperature of 225to 275° C. under autogenous pressure; wherein the fluoroetherfunctionalized aromatic diester or diacid is represented by thestructure (III),

wherein,Ar represents a benzene or naphthalene radical;each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl;OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II);R² is H or C₁-C₁₀ alkyl;X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the structure (Ia)

-   -   wherein q=0-10;    -   Y is O or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,        Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂;        and,        wherein the diamine comprises a C₄-C₁₂ linear alkylene diradical        which can be branched or unbranched wherein one or more carbons        can be replaced by ether oxygen, or a cyclic alkylene diradical        wherein one or more carbons can be replaced by ether oxygen;

In a further aspect, the present invention provides a shaped articlecomprising a polymer comprising a fluoroether functionalized aromaticrepeat unit represented by the structure (I)

wherein,wherein α is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen;Ar represents a benzene or naphthalene radical;each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl;OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II);wherein one or more carbons can be replaced by ether oxygen;X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the structure (Ia)

-   -   wherein q=0-10;    -   Y is O or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂.

DETAILED DESCRIPTION

When a range of values is provided herein, it is intended to encompassthe end-points of the range unless specifically stated otherwise.Numerical values used herein have the precision of the number ofsignificant figures provided, following the standard protocol inchemistry for significant figures as outlined in ASTM E29-08 Section 6.For example, the number 40 encompasses a range from 35.0 to 44.9,whereas the number 40.0 encompasses a range from 39.50 to 40.49.

The parameters n, p, and q as employed herein are each independentlyintegers in the range of 1-10.

As used herein, the term “fluoroether functionalized aromatic diester”refers to that subclass of compounds of structure (III) wherein R² isC₁-C₁₀ alkyl. The term “fluoroether functionalized aromatic diacid”refers to that subclass of compounds of structure (III) wherein R² is H.The term “perfluorovinyl compound” refers to the olefinicallyunsaturated compound represented by structure (VII), infra.

As used herein, the term “copolymer” refers to a polymer comprising twoor more chemically distinct repeat units, including dipolymers,terpolymers, tetrapolymers and the like. The term “homopolymer” refersto a polymer consisting of a plurality of repeat units that arechemically indistinguishable from one another.

In any chemical structure herein, when a terminal bond is shown as “—”,where no terminal chemical group is indicated, the terminal bond “—”indicates a radical. For example, —CH₃ represents a methyl radical.

In one aspect, the present invention provides a polymer comprising afluoroether functionalized aromatic repeat unit represented by thestructure (I).

wherein,α is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen;

-   -   Ar represents a benzene or naphthalene radical;    -   each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀        arylalkyl; OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II);wherein one or more carbons can be replaced by ether oxygen;X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the structure (Ia)

-   -   wherein q=0-10;    -   Y is O or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂.

As can be noted in the formulas above that show substituents attached toaromatic rings “Ar”, the substituents can be attached to the aromaticrings at any point, thus making it possible to have ortho-, meta- andpara-substituents as defined above.

In one embodiment of the polymer, one R is OH.

In one embodiment of the polymer, each R is H.

In one embodiment of the polymer, one R is OH and the remaining two Rsare each H.

In one embodiment of the polymer, one R is represented by the structure(II) and the remaining two Rs are each H.

In one embodiment of the polymer, α is a C₄-C₁₂ linear alkylenediradical which can be branched or unbranched.

In one embodiment of the polymer, α is an unbranched hexamethylenediradical.

In one embodiment of the polymer, X is O. In an alternative embodiment,X is CF₂.

In one embodiment of the polymer, Y is O. In an alternative embodiment,Y is CF₂.

In one embodiment of the polymer Z is Cl or Br. In a further embodiment,Z is Cl. In an alternative embodiment, one R is represented by thestructure (II), and one Z is H. In a further embodiment, one R isrepresented by the structure (II), one Z is H, and one Z is Cl.

In one embodiment of the polymer, Rf¹ is CF₂.

In one embodiment of the polymer, Rf² is CF₂.

In one embodiment of the polymer, Rf² is a bond (that is, p=0), and Y isCF₂.

In one embodiment, a=0.

In one embodiment, a=1, q=0, and n=0.

In one embodiment of the polymer, a=1, each R is H, Z is Cl, α isunbranched hexamethylene, X is O, Y is O, Rf¹ is CF₂, and Rf² isperfluoropropenyl, and q=1.

In one embodiment of the polymer, the polymer is a homopolymer.

In one embodiment, the polymer is a copolymer made up of repeat unitsthat are different embodiments of structure (I); that is, differentrepeat units that are still represented by embodiments of structure (I).The copolymer can thus contain repeat units of structure (I) that arethe same or different.

In one embodiment the specific repeat unit represented by structure (I)is represented by the structure (IVa)

wherein R, α, Z, X, Q, and a are as stated supra.

In one embodiment the specific repeat unit represented by structure (I)is represented by the structure (IVb)

whereinα is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen;Ar represents a benzene or naphthalene radical;each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl;OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II);wherein one or more carbons can be replaced by ether oxygen;X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the structure (Ia)

-   -   wherein q=0-10;    -   Y is O or CF₂;

Rf¹ is (CF₂)_(n), wherein n is 0-10;

-   -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂.

In an alternative embodiment, the polymer is a copolymer comprisingfluoroether functionalized aromatic repeat units represented by thestructure (IVa) and fluoroether functionalized aromatic repeat unitsrepresented by the structure (IVb). In one embodiment, the copolymer isa random copolymer. In one embodiment, the copolymer is a blockcopolymer.

In another embodiment the polymer is a copolymer further comprisingamide repeat units represented by the structure (V),

wherein α is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen; and, β is a C₄-C₁₂ linear alkylene diradicalwhich can be branched or unbranched wherein one or more carbons can bereplaced by ether oxygen, a cyclic alkylene diradical wherein one ormore carbons can be replaced by ether oxygen, or an aromatic radical.

In another embodiment, the polymer is a copolymer further comprisingamide repeat units represented by the structure (VIII)

wherein γ is a C₂-C₅ linear alkylene diradical that can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,a cyclic alkylene diradical wherein one or more cabons can be replacedby ether oxygen, or an aromatic radical. In a further embodiment, γ is(CH₂)₅.

In one embodiment, the copolymer is a random copolymer.

In another aspect, the present invention provides a process comprisingcombining in a pressure vessel a fluoroether functionalized aromaticdiester or diacid with a C₄-C₁₂ diamine, branched or unbranched, to forma reaction mixture; sealing said pressure vessel; and, heating saidreaction mixture in an oxygen reduced atmosphere to a temperature in therange of 225 to 275° C. under autogenous pressure; wherein thefluoroether functionalized aromatic diester or diacid is represented bythe structure (III),

wherein,Ar represents a benzene or naphthalene radical;each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl;OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II);R² is H or C₁-C₁₀ alkyl;X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the structure (Ia)

-   -   wherein q=0-10;    -   Y is O or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂;        and,        wherein the diamine comprises a C₄-C₁₂ linear alkylene diradical        which can be branched or unbranched wherein one or more carbons        can be replaced by ether oxygen, or a cyclic alkylene diradical        wherein one or more carbons can be replaced by ether oxygen

In one embodiment the diamine is a C₄-C₁₂ unbranched alkylene diradical.

In one embodiment the diamine is hexamethylene diamine.

In one embodiment of the process, one R is OH.

In one embodiment of the process, each R is H.

In one embodiment of the process, one R is OH and the remaining two Rsare each H.

In one embodiment of the process, one R is reperesented by the structure(II) and the remaining two Rs are each H.

In one embodiment of the process, R² is H.

In one embodiment of the process, R² is methyl.

In one embodiment of the process, X is O. In an alternative embodiment,X is CF₂.

In one embodiment of the process, Y is O. In an alternative embodiment,Y is CF₂.

In one embodiment of the process Z is Cl or Br. In a further embodiment,Z is Cl. In an alternative embodiment, one R is represented by thestructure (II), and one Z is H. In a further embodiment, one R isrepresented by the structure (II), one Z is H, and one Z is Cl.

In one embodiment of the process, Rf¹ is CF₂.

In one embodiment of the process, Rf² is CF₂.

In one embodiment of the process, Rf² is a bond (that is, p=0), and Y isCF₂.

In one embodiment, a=0.

In one embodiment, a=1, q=0, and n=0.

In one embodiment of the process, each R is H, Z is Cl, R² is methyl, Xis O, Y is O, Rf¹ is CF₂, Rf² is perfluoropropenyl, q=1, and the diamineis hexamethylene diamine.

Suitable diamines include but are not limited to 1,4-diaminobutane,1,4-diaminocyclohexane, 1,6-diaminohexane, 1,8-diaminooctane,1,10-diaminodecane, and 1,12-diaminododecane.

While a catalyst is not required to effect the process hereof, acatalyst can be optionally included in the reaction mixture. Suitablecatalysts include but are not limited to sodium hypophosphite,phenylphosphinic acid, sodium phenylphosphinate, and phosphoric acidalthough sometimes no catalyst is used. Other typical nylonpolymerization additives can also optionally be included in the reactionmixture. Suitable additives include but are not limited to antioxidants,pigments, and, end group modifiers.

The thus resulting polymer can be separated from the reacted reactionmixture by cooling the vessel and recovering the formed polymer plug.

In one embodiment the reaction mixture comprises more than oneembodiment of the repeat units encompassed in structure (I).

In another embodiment, the reaction mixture further comprises adicarboxylc acid or ester represented by the Structure (VI).

wherein β is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,a cyclic alkylene diradical wherein one or more carbons can be replacedby ether oxygen, or an aromatic radical; and wherein R⁴ is H or a C₁-C₄alkyl group. In a further embodiment, R⁴ is H and each R is H. In analternative embodiment, R⁴ is methyl and each R is H.

In one embodiment, β is an unbranched hexamethylene diradical but couldinclude any other odd or even numbered, branched or non-branchedaliphatic diradical.

In an alternative embodiment the reaction mixture further comprises alactam. In a further embodiment, the reaction mixture further comprisescaprolactam.

Suitable fluoroether functionalized aromatic diesters can be prepared byforming a reaction mixture comprising a hydroxy aromatic diester in thepresence of a solvent and a catalyst with a perfluoro vinyl compoundrepresented by the structure (VII)

wherein X is O or CF₂, a=0 or 1; and, Q represents the structure (Ia)

-   -   wherein q=0-10;

Y is O or CF₂;

Rf¹ is (CF₂)_(n), wherein n is 0-10;

Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when p is 0,Y is CF₂;

at a temperature between about −70° C. and the reflux temperature of thereaction mixture.

Preferably the reaction is conducted using agitation at a temperatureabove room temperature but below the reflux temperature of the reactionmixture. The reaction mixture is cooled following reaction.

When a halogenated solvent is employed, the group indicated as “Z” inthe resulting fluorovinyl ether aromatic diester represented bystructure (III) is the corresponding halogen. Suitable halogenatedsolvents include but are not limited to tetrachloromethane,tetrabromomethane, hexachloroethane and hexabromoethane. If the solventis non-halogenated Z is H. Suitable non-halogenated solvents include butare not limited to tetrahydrofuran (THF), dioxane, and dimethylformamide(DMF).

The reaction is catalyzed by a base. A variety of basic catalysts can beused, i.e., any catalyst that is capable of deprotonating phenol. Thatis, a suitable catalyst is any catalyst having a pKa greater than thatof phenol (9.95, using water at 25° C. as reference). Suitable catalystsinclude, but are not limited to, sodium methoxide, calcium hydride,sodium metal, potassium methoxide, potassium t-butoxide, potassiumcarbonate or sodium carbonate. Preferred are potassium t-butoxide,potassium carbonate, or sodium carbonate.

Reaction can be terminated at any desirable point by the addition ofacid (such as, but not limited to, 10% NCl). Alternatively, when usingsolid catalysts, such as the carbonate catalysts, the reaction mixturecan be filtered to remove the catalyst, thereby terminating thereaction.

Suitable hydroxy aromatic diesters include, but are not limited to,1,4-dimethyl-2-hydroxy terephthalate, 1,4-diethyl-2-5-dihydroxyterephthalate, 1,3-dimethyl 4-hydroxyisophthalate,1,3-dimethyl-5-hydroxy isophthalate, 1,3-dimethyl 2-hydroxyisophthalate,1,3-dimethyl 2,5-dihydroxyisophthalate, 1,3-dimethyl2,4-dihydroxyisophthalate, dimethyl 3-hydroxyphthalate, dimethyl4-hydroxyphthalate, dimethyl 3,4-dihydroxyphthalate, dimethyl4,5-dihydroxyphthalate, dimethyl 3,6-dihydroxyphthalate, dimethyl4,8-dihydroxynaphthalene-1,5-dicarboxylate, dimethyl3,7-dihydroxynaphthalene-1,5-dicarboxylate, dimethyl2,6-dihydroxynaphthalene-1,5-dicarboxylate, or mixtures thereof.

Suitable perfluorovinyl compounds include, but are not limited to,1,1,1,2,2,3,3-heptafluoro-3-(1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluorovinyloxy)propan-2-yloxy)propane,heptafluoropropyltrifluorovinylether, perfluoropent-1-ene,perfluorohex-1-ene, perfluorohept-1-ene, perfluorooct-1-ene,perfluoronon-1-ene, perfluorodec-1-ene, and mixtures thereof.

To prepare a suitable fluoroether functionalized aromatic diester asuitable hydroxy aromatic diester and a suitable perfluovinyl compoundare combined in the presence of a suitable solvent and a suitablecatalyst until the reaction has achieved the desired degree ofconversion. The reaction can be continued until no further product isproduced over some preselected time scale. The required reaction time toachieve the desired degree of conversion depends upon the reactiontemperature, the chemical reactivity of the specific reaction mixturecomponents, and the degree of mixing applied to the reaction mixutre.Progress of the reaction can be monitored using any one of a variety ofestablished analytical methods, including, but not limited to, nuclearmagnetic resonance spectroscopy, thin layer chromatography, and gaschromatography.

When the desired level of conversion has been achieved, the reactionmixture is quenched, as described supra. The thus quenched reactionmixture can be concentrated under vacuum, and rinsed with a solvent.Under some circumstances, a plurality of compounds encompassed by thestructure (III) can be made in a single reaction mixture. In such cases,separation of the products thus produced can be effected by any methodknown to the skilled artisan such as, but not limited to, distillationor column chromatography.

If it is desired to employ the corresponding diacid as the monomerinstead of the diester, the thus produced fluorovinyl etherfunctionalized aromatic diester can be contacted with an aqueous base,preferably a strong base such as KOH or NaOH, at a gentle reflux,followed by cooling to room temperature, followed by acidifying themixture, preferably with a strong acid, such as HCl or H₂SO₄, until thepH is between 0 and 2. Preferably pH is 1. The acidification thusperformed causes the precipitation of the fluorovinyl etherfunctionalized aromatic diacid. The thus precipitated diacid can then beisolated via filtration and recrystallization from suitable solvents(e.g., redissolved in a solvent such as ethyl acetate, and thenrecrystallized). The progress of the reaction can be followed by anyconvenient method, including but not limited to thin layerchromatography, gas chromatography and NMR.

Once the fluoroether aromatic compound has been prepared, it is suitablefor polymerization, among other potential uses.

In a further aspect, the present invention provides a shaped articlecomprising a polymer comprising a fluoroether functionalized aromaticrepeat unit represented by the structure (I)

wherein,α is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen;Ar represents a benzene or naphthalene radical;each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀ arylalkyl;OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II);wherein one or more carbons can be replaced by ether oxygen;X is O or CF₂;Z is H, Cl, or Br;a=0 or 1;and,Q represents the structure (Ia)

-   -   wherein q=0-10;    -   Y is O or CF₂;    -   Rf¹ is (CF₂)_(n), wherein n is 0-10;    -   and,    -   Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when        p is 0, Y is CF₂.

In one embodiment, the shaped article is a film or sheet.

In another embodiment, the shaped article is a fiber or an articlecomprising said fiber.

In still another embodiment, the shaped article is a container, such asa bottle, tubing, and other such articles as can be formed in moldingoperations.

The shaped articles hereof are fabricated from the melt by any processcommonly employed in preparing shaped articles of thermoplasticpolymers, including but not limited to compression molding, injectionmolding, screw extrusion, and fiber spinning.

The invention is further described but not limited by the followingspecific embodiments.

EXAMPLES

The chemicals and reagents were used as received in the Examples asfollows:

From Sigma-Aldrich, Milwaukee, Wis.:

-   -   potassium t-butoxide    -   tetrahydrofuran (THF)    -   dichloromethane    -   hydrochloric acid (HCl)    -   anhydrous sodium sulfate    -   dimethyl 5-hydroxyisophthalate    -   potassium hydroxide (KOH)    -   caprolactam        From SynQuest Labs., Alachua, Fla.:    -   heptafluoropropyltrifluorovinylether        From Invista Intermediates    -   adipic acid    -   1,6 diamino hexane

Examples 1-4 A. Preparation of dimethyl5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)isophthalate (F10-iso)

In a dry box, dimethyl 5-hydroxyisophthalate (63.0 g, 0.300 mol) wasadded to an oven-dried multiple neck reaction flask equipped with astirring bar and a pressure equaling (PE) addition funnel.Tetrahydrofuran (THF, 1500 mL) was then added to the reaction flask, andthe reaction mixture was stirred until a homogeneous solution resulted.Potassium t-butoxide (9.24 g, 0.0825 mol) was added to the reactionmixture, resulting in a heterogeneous mixture. Via the PE funnel,heptafluoropropyltrifluorovinyl ether (199.2 g, 0.075 mol) was added tothe reaction flask to form a reaction mixture. The reaction mixture wasallowed to stir at room temperature for ˜24 hours. The reaction wasquenched by the addition for 80 mL of 10% HCl to the reaction flask toform a reaction material. The resulting material was concentrated atreduced pressure. The material was then dissolved in dichloromethane(˜150 mL) and then washed with 10% HCl (2×100 mL) and then with water(˜100 mL) to form an organic phase and an aqueous phase. The separatedorganic phase was then dried over anhydrous sodium sulfate. The sodiumsulfate was then filtered off and the resulting material containing acrude product was concentrated at reduced pressure. The crude productwas purified by column chromatography resulting in 100.87 g (70.63%)yield of the desired material, dimethyl5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)isophthalate.

B. Preparation of Random Copolyamide

Adipic acid, 1,6-diaminohexane (HMD), carbowax antifoam (5 mg to eachtube), dimethyl 5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)isophthalate (F10-iso), prepared supra were weighed in the amounts shownin Table 1 into 4 tubes that were capped on one end. The tubes were 14inches long and 1 inch in diameter, and made of stainless steel. HMD wasused as a 78 wt % solution in water. Approximately 20 grams of water wasadded to each tube. Each tube was connected to its own Grove valve(Grove Valve and Regulator Company, Oakland, Calif.) which regulated thepressure in each tube from a common control. The 4 tubes were initiallyheated to 130° C. at atmospheric pressure with a sand bath to purge airfrom the tubes with steam after which the release pressure on the Grovevalves was increased to 250 psi. The tubes were heated to 250° C. over aperiod of one hour. When they reached about 220° C. steam began to ventfrom the tubes through the Grove valves set to vent at 250 psig. Whenthe tubes reached 250° C. controlled pressure reduction was initiatedwhich ramped the pressure from 250 psig to atmospheric over one hour.During pressure reduction the tubes were heated to 275° C. The tubeswere heated for an additional 45 minutes at atmospheric pressure and275° C. before cooling. When the tubes were cool, they were opened andthe polymer was removed. The polymer was characterized by Size ExclusionChromatography (SEC) to determine weight average molecular weight(M_(w)) and Intrinsic Viscosity (IV), by Differential Scanningcalorimetry (DSC) to determine the glass transition temperature (T_(g))and melting point (T_(m)), and by NMR to confirm composition.

Results are shown in Table 2. The column labeled “monomer ratio” inTable 2 refers to the molar ratio of fluorine-containing monomer unitsto non-fluorine containing monomer units (formed from adipic acid andHMD). Note that the polymer of Example 4 did not exhibit a meltingtransition.

¹H-NMR (DCOOD) δ: 8.35 (ArH), 7.95 (ArH), 7.70 (NH), 6.60 (d, CFH), 3.55(—CH₂—NH—), 3.40 (—CH₂—NH—), 2.50 (—CH₂—CO—), 1.75 (—CH₂—), 1.60(—CH₂—), 1.40 (—CH₂—).

TABLE 1 Adipic HMD Acid (78% in H₂O) F10-iso (g) (g) (g) Example 1 12.6513.78 2.17 Example 2 10.82 12.46 3.92 Example 3 7.40 10.27 8.04 Example4 3.89 8.13 12.67

TABLE 2 Monomer M_(w) T_(g) T_(m) IV Ratio (D) (° C.) (° C.) (dL/g)Example 1 0.018 21,100 58.9 257.0 0.703 Example 2 0.048 20,600 59.1250.6 0.587 Example 3 0.2 36,800 58.7 198.6 0.455 Example 4 0.83 80,00074.1 / 0.456

Examples 5-8 A. Preparation of5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)isophthalic acid (F10diacid)

Dimethyl 5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalate(47.6 g, 0.10 mol) was added to a solution of water (1.00 L) and KOH(206 g, 3.5 mol). The resulting solution was heated to reflux for about48 hours. The reaction was cooled to room temperature and then acidifiedto a pH of about 1 with concentrated HCl. The precipitate material wasfiltered and then dried under vacuum for 4 days to give 38.51 g ofproduct.

B. Preparation of Random Copolyamide

The materials and procedures of Examples 1-4 were employed with theexception that caprolactam was employed in place of adipic acid and5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalic acid wasemployed in place of dimethyl5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy) isophthalate.

The amounts of ingredients used are shown in Table 3. Characterizationmethods were the same as in Examples 1-4. Results are shown in Table 4.The column labeled “monomer ratio” in Table 4 refers to the molar ratioof fluorine-containing monomer units to non-fluorine containing monomerunits (formed from caprolactam). Note that the polymers of Examples 7and 8 did not exhibit a melting transition.

¹H-NMR (DCOOD) δ: 8.35 (ArH), 7.95 (ArH), 7.70 (NH), 6.60 (d, CFH), 3.55(—CH₂—NH—), 3.40 (—CH₂—NH—), 2.45 (—CH₂—CO—), 1.90-1.30 (—CH₂—).

TABLE 3 HMD Caprolactam (78% in H₂O) F10-iso (g) (g) (g) Example 5 17.800.62 1.86 Example 6 15.88 1.16 3.49 Example 7 11.25 2.57 7.42 Example 8 6.00 4.05 11.88

TABLE 4 Monomer M_(w) T_(g) T_(m) IV Ratio (D) (° C.) (° C.) (dL/g)Example 5 0.024 29 900 56.8 206.6 0.794 Example 6 0.053 37 600 57.6186.7 0.752 Example 7 0.157 37 300 66.2 / 0.585 Example 8 0.51  75 80083.5 / 0.437

C. Preparation of Films and Contact Angle Measurements

A Pasadena hydraulic platen press was used to prepare compression moldedfilms. The temperature of the platens was set at 5 C above the meltingpoint of each sample. Melting points were determined using differentialscanning calorimetry, wherein the temperature at the peak of the meltingendotherm was selected as the melting point.

FIG. 1 depicts the sample preparation configuration as viewed incross-section. A sample of resin powder, 1, prepared as described suprawas placed in a 2″×4″×0.020″ mold, 2, formed from 0.020″ aluminum shimstock. The shim stock and resin powder were sandwiched between twosheets of fiberglass-reinforced Teflon® sheets, 3, to form a firstsandwich. The first sandwich was then placed between two polished brassplates, 4, to form a second sandwich. The second sandwich so formed wasplaced between the pre-heated platens of a hydraulic press. The presswas closed but no pressure was indicated on the pressure gauge. Thesecond sandwich was heated thus for 2 minutes. The press was thenopened, and the sample removed after cooling. The dimensions of theresultant film after trimming was about 1″×3″×0.020″. The film was thencut into strips ¼″×3″.

Static contact angles were recorded on a Rame'-Hart Model 100-25-Agoniometer (Rame'-Hart Instrument Co.) with an integrated DROPimageAdvanced v2.3 software system. A micro syringe dispensing system wasused to dispense 4 microLiters of either water or hexadecane onto thesurface of a film specimen as prepared supra. A compression molded filmof nylon 6 was used as a control. Results are shown in Table 5. Notethat hexadecane was observed to fully wet the nylon 6 control.

TABLE 5 Static Static water hexadecane contact contact angle (°) angle(°) Nylon-6 63.9 <10     Example 5 67.1 21.8 Example 6 75.8 27.7

Examples 9-11 A. Preparation of Random Copolyamide

The materials and procedures of Examples 1-4 were employed with theexception that 5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)isophthalicacid was employed in place of dimethyl5-(1,1,2-trifluoro-2-(perfluoropropoxy)ethoxy)isophthalate.

The amounts of ingredients used are shown in Table 6. Characterizationmethods were the same as in Examples 1-4. Results are shown in Table 7.

¹H-NMR (DCOOD) δ: 8.35 (ArH), 7.95 (ArH), 7.70 (NH), 6.60 (d, CFH), 3.55(—CH₂—NH—), 3.40 (—CH₂—NH—), 2.50 (—CH₂—CO—), 1.75 (—CH₂—), 1.60(—CH₂—), 1.40 (—CH₂—).

TABLE 6 Adipic HMD Acid (78% in H₂O) F10-diacid (g) (g) (g) Example 911.50 12.54 1.86 Example 10 10.26 11.82 3.49 Example 11 6.87 9.54 7.02

TABLE 7 Fluorine final M_(w) T_(g) T_(m) IV F_(mol)/CL_(mol) (D) (° C.)(° C.) (dL/g) Example 9 0.051  11 300 58.4 253.5 0.448 Example 10 0.11  50 600 60.7 246.3 0.932 Example 11 0.31  172 000 72.1 218.4 1.146

B. Preparation of films and contact angle measurements from fluorinatedpolyamides was done as for Example 5 and Example 6

For results see Table 8. In this case a control film was made from Zytel101 nylon 6,6 available from The DuPont Company.

TABLE 8 Static Static water hexadecane contact contact Sample name angle(°) angle (°) control 85 <10¹   Example 9 91.3 15.2 Example 10 124.527.2

1. A polymer comprising a fluoroether functionalized aromatic repeatunit represented by the structure (I)

wherein, is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen; Ar represents a benzene or naphthaleneradical; each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀arylalkyl; OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II), X is O or CF₂; Z is H, Cl, or Br; a=0 or 1; and, Qrepresents the structure (Ia)

wherein q=0-10; Y is O or CF₂; Rf¹ is (CF₂)_(n), wherein n is 0-10; and,Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when p is 0,Y is CF₂.
 2. The polymer of claim 1 wherein each R is H.
 3. The polymerof claim 1 wherein one R is a radical represented by the structure (II)and the remaining two Rs are each H.
 4. The polymer of claim 1 whereinis a C₄-C₁₂ alkylene diradical which can be branched or unbranched. 5.The polymer of claim 1 wherein is an unbranched hexamethylene diradical.6. The polymer of claim 1 wherein X is O.
 7. The polymer of claim 1wherein Y is O.
 8. The polymer of claim 1 wherein Z is Cl.
 9. Thepolymer of claim 1 wherein, Rf¹ is CF₂.
 10. The polymer of claim 1wherein Rf² is CF₂.
 11. The polymer of claim 1 wherein p=0, and Y isCF₂.
 12. The polymer of claim 1 wherein X is CF₂, a=1, q=0, and n=0. 13.The polymer of claim 1 wherein the repeat unit is represented by thestructure (IVb)

wherein is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen; Ar represents a benzene or naphthaleneradical; each R is independently H, C₁-C₁₀ alkyl, C₅-C₁₅ aryl, C₆-C₂₀arylalkyl; OH, or a radical represented by the structure (II)

with the proviso that only one R can be OH or the radical represented bythe structure (II), X is O or CF₂; Z is H, Cl, or Br; a=0 or 1; and, Qrepresents the structure (Ia)

wherein q=0-10; Y is O or CF₂; Rf¹ is (CF₂)_(n), wherein n is 0-10; and,Rf² is (CF₂)_(p), wherein p is 0-10, with the proviso that when p is 0,Y is CF₂.
 14. The polymer of claim 1 further comprising amide repeatunits represented by the structure (V),

wherein is a C₄-C₁₂ linear alkylene diradical which can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,or a cyclic alkylene diradical wherein one or more carbons can bereplaced by ether oxygen; and, is a C₄-C₁₂ linear alkylene diradicalwhich can be branched or unbranched wherein one or more carbons can bereplaced by ether oxygen, a cyclic alkylene diradical wherein one ormore carbons can be replaced by ether oxygen, or an aromatic radical.15. The polymer of claim 13 wherein, a=1, each R is H, Z is Cl, is anunbranched hexamethylene diradical, X is O, Y is O, Rf¹ is CF₂, and Rf²is perfluoropropenyl, and q=1.
 16. The polymer of claim 1 furthercomprising amide repeat units represented by the structure (VIII)

wherein is a C₂-C₅ linear alkylene diradical that can be branched orunbranched wherein one or more carbons can be replaced by ether oxygen,a cyclic alkylene diradical wherein one or more cabons can be replacedby ether oxygen, or an aromatic radical.
 17. The polymer of claim 16wherein is (CH₂)₅.